Styrene type monomers containing substituents thereon, e.g. urea, and polymers and copolymers thereof

ABSTRACT

A plurality of substituted styrene monomers, for example, urea substituted, is disclosed as well as polymers and copolymers made therefrom. Various thermoset plastic components can be reacted with the monomers, polymers, or copolymers of these substituted styrenes, as for example epoxy, which form a crosslinked system useful as an adhesive or a fiber reinforced substrate for circuit boards. The monomers are made by reacting aminostyrene type monomers with isocyanate containing molecules. One specific monomer is made by reacting a substituted aminostyrene with a monoisocyanate and has the following formula ##STR1##

FIELD OF THE INVENTION

The present invention relates to the preparation of substituted styrenetype monomers as from the reaction of an alpha-substituted aminostyrenewith various isocyanates, for example monoisocyanate, diisocyanate,etc., and to the free radical or thermal polymerization productsthereof. The reaction product of the amino substituted styrene andisocyanate compounds can be further reacted into thermoset plasticscompositions having functional groups reactive with the amine orisocyanate.

BACKGROUND OF THE INVENTION

Various compounds having amino-substituted benzene rings have beendisclosed in the literature.

SUMMARY OF THE INVENTION

It is an aspect of this invention to create various amino-substitutedstyrene compounds and polymers made therefrom that can be reacted withother materials through either the vinylic unsaturation, the aminogroup, or through other functional groups attached through the aminogroup.

Various substituted styrene type monomers are formed by the reaction ofat least one alpha-substituted aminostyrene with at least oneisocyanate, for example a monoisocyanate, a diisocyanate, etc. Thereaction generally proceeds at ambient temperature typically in an inertatmosphere under moisture-free conditions. The mole ratio of theisocyanate to the alpha-substituted aminostyrene to the isocyanatecompound can vary greatly such as from 0.3 to 4. If one or moremonoisocyanate compounds are utilized, the mole ratio of theaminostyrene to the monoisocyanate compound(s) can vary. However, whenthe isocyanate compound is a diisocyanate, a triisocyanate, etc., orblends thereof, the ratio of the polyisocyanate to the styrene isgenerally stoichiometric if the desired product is to have residualunreacted isocyanate groups. If a compound or monomer is desired suchthat it generally has aminostyrene end groups, an excess of theaminostyrene groups is generally used. Inasmuch as blends of variouspolyisocyanates can be utilized along with monoisocyanates and widelydifferent mole ratios, a great variety (e.g. a statistical stew) ofmonomers can be produced by the reaction product of one or moreisocyanate compounds with one or more alpha-substituted aminostyrenecompounds. Both reactants generally are a liquid so that no solvent isgenerally required. The reaction products are usually a solid at roomtemperature.

The various monomers made from the reaction of isocyanates withaminostyrene molecules, which are generally solids can be polymerized byeither melt polymerization or solution polymerization. In meltpolymerization, the monomers are generally heated to the above meltingpoint of the monomer. In either polymerization process, an inertatmosphere is generally utilized.

The above polymers and their monomers can be further reacted with otherthermoset plastic components such as epoxies. Once such component is anepoxy resin which can be utilized in an amount of from about 1 percentto about 99 percent by weight based upon the total weight of the epoxyresin and the polymer.

DETAILED DESCRIPTION

According to the present invention, numerous different monomers can beformed which are the reaction product of one or more alpha-substitutedaminostyrenes ##STR2## and one or more polyisocyanates having theformula R² --(NCO)_(x), where x represents the average number of NCOgroups and is any number or fraction thereof from about 1 to about 4.The type of monomer formed by the reaction product will vary with themole ratio of aminostyrene to the isocyanate compound. During someactions, as will be better understood by reference to the descriptionherein-below, no single particular reaction product will be formed butrather two or more products can be formed, often times the result ofcompeting reactions, or the like. In effect, some of the monomerreaction end products will be a statistical stew.

The R¹ substituent of the styrene compound can be hydrogen, an aliphaticand preferably an alkyl having from 1 to 44 carbon atoms, a halogen suchas fluorine, chlorine, bromine, iodine, or an aryl or an alkylsubstituted aryl having a total of from 6 to 40 carbon atoms withspecific examples including diphenyl, naphthyl, anthracene, decacyclene,and the like, desirably an alkyl having from 1 to 18 carbon atoms, moredesirably from 1 to 8 carbon atoms, and preferably methyl. Hydrogen andmethyl are highly preferred. The amine group can be in the ortho, meta,or para position on the benzene ring with the para position substitutionbeing preferred.

With regard to the isocyanate compound, as noted above, x can vary fromabout 1 to about 4, and desirably from about 1 to about 3. Thus, theisocyanate compound can be a monoisocyanate, a diisocyanate, atriisocyanate, or any blend thereof, as for example where x isapproximately 2.5, that is approximately 1/2 diisocyanate and 1/2triisocyanate. R² can be an aliphatic such as an alkyl containing from 2to 20 carbon atoms, a cycloaliphatic such as a cycloalkyl having from 4to 20 carbon atoms, an aromatic or an alkyl substituted aromatic havingfrom 6 to 20 carbon atoms, an aromatic substituted alkyl having from 6to 20 carbon atoms, or combinations thereof. Examples of monoisocyanatesinclude phenyl isocyanate, o-tolyl isocyanate, m-tolyl isocyanate,p-tolyl isocyanate, and n-butyl isocyanate. Examples of polyisocyanatesinclude 4,4'-methylene-bis-(phenyl isocyanate) (MDI); m-xylylenediisocyanate (XDI), phenylene-1,4-diisocyanate,naphthalene-1,5-diisocyanate,diphenylmethane-3,3'-dimethoxy-4,4'-diisocyanate and toluenediisocyanate (TDI); as well as aliphatic diisocyanates such ashexamethylene diisocyanate, octyl decyl diisocyanate, isophoronediisocyanate (IPDI), 1,4-cyclohexyldiisocyanate (CHDI),decane-1,10-diisocyanate, and dicyclohexylmethane-4,4'-diisocyanate,1,6-diisocyanatohexane, dicyclohexamethane-4,4'-diisocyanate(hydrogenated MDI). Generally, 1,6-diisocyanatohexane is preferred. Whenthe final product needs high temperature stability, then aromaticisocyanates are preferred.

The isocyanate compounds can also be the reaction product of theabove-mentioned polyisocyanates where x is about 2 to about 3, and lowmolecular weight polyols or polyamines. The polyols are desirablypoly(alkylene oxides) or polyesters well known to the art. Preferably,the polyols and polyamines are diols or diamines. The molecular weightof the polyols and polyamines are desirably less than 300. The polyolsand polyamines desirably are composed of atoms selected from hydrogen,carbon, nitrogen and oxygen. The reaction product of the aminostyrenesand the isocyanates may also be post reacted with said polyols or saidpolyamines if there are residual unreacted isocyanate groups after thefirst reaction.

The reaction product of one or more aminostyrenes with one or moremonoisocyanates may yield one or more compounds of the formula ##STR3##where R¹ and R² are as noted above,

The mole ratio of monoisocyanate to the alpha-substituted aminostyreneis desirably from about 0.5 to about 1.5 with from about 0.9 to about1.1 being preferred. Since both compounds are generally liquid atambient temperature, a solvent is not utilized. The reaction generallyoccurs at low temperatures but above the melting point of the reactants,and generally from about -30° C. to about 100° C., desirably from about-20° C. to about 50° C. with from about -5° C. to about 5 or 30° C.being preferred under atmospheric pressure. An inert or dry atmosphereis preferably utilized such as nitrogen so that the reaction is free ofwater or moisture.

If the one or more polyisocyanates are diisocyanates, and generally aequal mole amounts of each reactant are utilized, the reaction productis generally represented by formula III ##STR4## where R¹ and R² are asset forth above.

If the polyisocyanate compound is a triisocyanate, a monomer is madewhich can generally be represented by formula IVA ##STR5## where R¹ andR² are as set forth above.

A monomer can be made generally represented by formula IVB utilizing twodiisocyanates, that is the reaction of two individual diisocyanates,either the same or different, wherein the diisocyanates reacts off ofthe amine group. ##STR6##

It should be appreciated to one skilled in the art that a large numberof monomers can be made by utilizing a singe specific type ofaminostyrene compound as well as a specific type of a polyisocyanate. Ofcourse, when a mixture of two or more different types of aminostyrenecompounds are utilized and/or a mixture of two or more different typesof polyisocyanates, a vast number of monomer blends containing two ormore different types of monomers therein are produced. The amount of aspecific type of monomer within a particular monomer blend will varydepending upon the amount of initial components utilized as well as theresult of completing reactions. Generally, monomers made from oneaminostyrene compound and one polyisocyanate compound such as those setforth in formulas III and IV are desired.

The mole ratio of the polyisocyanate compound to the para-aminostyrenecompound utilized to form the formula III and IVA type compounds isdesirably from about 0.80 to about 1.80 and preferably from 0.90 or 0.98to about 1.1 or 1.5. The reaction conditions for formation of theformula III and IVA monomers are generally very similar to the formationof the formula II monomer as set forth hereinabove and thus the same isfully incorporated and not repeated for sake of brevity.

When two diisocyanates are utilized to form a monomer having anallophanate-like group therein, e.g., formula IVB, the mole ratio of thepolyisocyanate, that is diisocyanate to the para-aminostyrene compoundis desirably from about 1.8 to about 4.0 and preferably from about 2.0to about 2.5. The reaction conditions are once again generally the samewith regard to the formulation of the formula II monomer as set forthhereinabove.

If an excess of the aminostyrene compound is utilized, that is a molarratio deficiency of the polyisocyanate is utilized, the residualisocyanate end groups will react with the excess aminostyrene. Dependingupon the excess of the aminostyrene compound, a blend of isocyanateterminated monomers will exist as well as a monomer generally endcappedby two aminostyrene groups, that is a monomer which generally has twourea groups therein as well as two styrene groups therein whichgenerally can be represented by formula VA. ##STR7## wherein R¹ and R²are as set forth hereinabove. R³ independently is R¹ and therefore canbe hydrogen, an aliphatic having from 1 to 44 carbon atoms, a halogen,an aryl or an alkyl substituted aryl having from 6 to 40 carbon atoms,and the like. Accordingly, R³, independently, can be the same ordifferent than R¹. The molar ratio utilized to produce at least a smallamount of the formula VA type monomer requires a slight excess of theaminostyrene and, hence, the molar ratio of polyisocyanate to theaminostyrene is more desirably from about 0.33 to about 0.78, anddesirably from about 0.46 to about 0.49. The reaction conditions are thesame as set forth above for the other formulas.

Another and preferred way of making formulation VA relates to utilizingthe method of making formula III and subsequently reacting formula IIIwith the paraaminostyrene of formula I. In this embodiment, the variousmole ratios and reaction conditions for making the formula III compoundare the same as set forth above and the ratio of the para-aminostyreneto the compound of formula III is up to 1.5, and desirably is up toabout 1.0 or 1.1. The reaction conditions are similar to the otherreactions to form compounds of formula II through IVA.

Other monomers which can be formed if an excess of aminostyrene compoundis utilized is set forth by formula VB and VC. The compound of formulaVB is made by using 3 moles of aminostyrene and desirably from about1.75 to about 2.25, preferably about 2 moles of a diisocyanate.Alternatively, this compound can be made from 1 mole of the compound offormula IVB reacted with 2 moles of aminostyrene. R¹, R², and R³ canindependently be the same moieties as in previous structures. When morethan one R³ appears in a structure, R³ can be different moieties withinthat structure. The reaction conditions are similar to those above. Themolar ratios of the reactants can vary by 20 to 40 mole percent tocompensate for reactivity differences between the reactants. Thecompound of formula VC is made from a triisocyanate and about threeaminostyrene molecules. ##STR8##

The reaction conditions for producing monomers which generally have twoor more styrene groups on the end portions thereof or a blend of thesame with monomers of the type set forth in formulas III and IV are thesame as set forth hereinabove. That is, generally the reaction occurs atlow temperatures as from about -30° C. to about 100° C. without the useof any catalyst.

It should once again be apparent that a large number of specificmonomers can be produced having at least a portion of the formula VA, VBand/or VC compounds therein, that is from at least 1 percent up to 100weight percent. A mixture of two or more different types of aminostyrenecompounds can be utilized and/or a mixture of two or more differenttypes of polyisocyanates are utilized.

Thus, as apparent from the preceding discussion, a host or a myriad ofdifferent types of monomers can be formed according to the presentinvention and often times the resulting reaction product is a so-calledstatistical stew. Examples of specific monomers which are preferredinclude o, m and p-tolyl urea styrene; hexyl diurea styrene, butyl ureastyrene, octadecyl urea styrene, phenyl urea styrene, and 1,6-hexylisocyanate urea styrene. These type monomers will be referred to hereinby the term monomers derived from aminostyrene.

The above monomers whether made from one or more isocyanate compoundsare generally amphiphilic and thus can be utilized in forming emulsionsas well as for controlling the structure of liquid crystals. The abovemonomers can also be utilized as crosslinking agents, as coatings, asadhesives, and as thermosets, as well as intermediates for formingsizing agents and the like.

Since all of the above monomers have unsaturation sites therein, theycan readily be solution or melt polymerized by free radical, cationic oranionic polymerization. The use of these monomers in anionicpolymerization may benefit from protecting groups as disclosed in J.Polym. Sci.; Polym. Lett. Ed., 21, p 395 (1983) which is herebyincorporated by reference.

When polymerized according to melt polymerization, the various abovedescribed monomers are heated above their melting point generally in theabsence of any solvent as well as the absence of any initiator/catalystand are readily polymerized. These amino styrene monomers similar tostyrene monomers are believed to be capable of self-initiatedpolymerization. Melt polymerization is preferred and can be conductedafter epoxy oligomers have reacted with the monomers of this invention.The polymerization occurs readily at temperatures 10° C. or more abovethe melting temperature of the monomers or desirably above 150° C. orpreferably from 190° C. to 250° C. The various above styrene class ofmonomers are readily melt polymerized through reaction of the vinylgroup and thus contains pendent urea or isocyanate groups thereon. Allthe polymerizations are preferably conducted in an inert atmosphere.

Although generally only one specific type of monomer is polymerized, itis within the scope of the present invention to polymerize blends of thesame type of monomers, for example blends formula II type compounds,blends of formula III type compounds, blends of formula V typecompounds, blends of formula VI type compounds, and the like. Moreover,blends of monomers represented by two or more different formulas IIthrough V, such as formulas II and III, formulas III and V, etc. canalso be utilized. It should thus be apparent that a very large number ofpolymers can be produced according to the scope of the presentinvention.

Free radical polymerization can also be carried out in the presence of asolvent. The solvent is generally an organic compound which has aboiling point greater than the polymerization temperature. Free radicalpolymerization of the above-noted compounds of the present inventiongenerally occurs at a temperature range of from about 40° to about 150°C., desirably from about 50° to about 100° C. and preferably from about50° to about 70° C. Suitable solvents include various aromatic compoundsor alkyl substituted aromatic compounds having a total of from 6 to 20carbon atoms, with specific examples include benzene, xylene, toluene,cresol, and the like. Various aliphatic compounds can be utilized suchas the various alkanes having from 6 to about 10 carbon atoms, withspecific examples including hexane, petroleum, ether (i.e., mostlyheptane), and the like. Chlorinated aliphatic compounds such aschlorinated alkyl compounds having a total of from about 1 to about 5carbon atoms can also be utilized with specific examples includingchloroform, methylene chloride, and the like. The various ketones havingfrom 3 to about 10 carbon atoms can also be utilized such as acetone,methyl ethyl ketone, methyl isobutylketone, and the like. Alcoholshaving from 1 to 5 carbon atoms can also be utilized such as methylalcohol, ethyl alcohol, isopropyl alcohol, and the like.

The free radical initiator which is utilized to polymerize theabove-noted monomers can generally be any catalyst well known to the artand to the literature. For example, various organic peroxides, acylperoxides, peresters, and hydroperoxides can be utilized such as benzoylperoxide, dicumyl peroxide, cumene hydroperoxide, paramethanehydroperoxide, acetyl peroxide, t-butyl perbenzoate, and the like, usedalone or with redox systems. Diazo compounds such asazobisisobutyronitrile (AIBN), and the like; persulfate salts such assodium, potassium, and ammonium persulfate, used alone or with redoxsystems; and ultraviolet light with photo-sensitive agents such asbenzophenone, triphenylphosphine, organic diazos, and the like may beused as the free radical initiator. Generally, AIBN is preferred. Thefree radical catalyst must be soluble in a solvent and the amountthereof present is generally up to about 2.0, desirably from about 0.001to about 2.0 parts by weight, and preferably from about 0.001 to about0.01 parts by weight for every 100 grams of the monomer.

In lieu of free radical polymerization, anionic polymerization can beutilized. Therein naphthalene sodium, n-butyl lithium, or other anionicinitiators well known to the art and to the literature are used. Throughthe use of anionic polymerization systems, the molecular weight can becontrolled in a rather precise manner. In such polymerization systems,an inert gas such as nitrogen is generally utilized to removecontaminates such as water, moisture, carbon dioxide, and the like.Anionic polymerizations are generally carried out at very lowtemperatures such as from about -70° C. to about 50° C., and desirablyfrom about -40° C. to about -20° C.

The various monomers discussed hereinabove can also be generallypolymerized via cationic polymerization. The cationic polymerizationsystem can produce polymers of molecular weights up to a few thousand ifinitiated by strong acids such as perchloric, sulfuric, phosphoric,fluoro- and chlorosulfonic, methanesulfonic, andtrifluoromethanesulfonic. Polymerizations using these initiators can beperformed up to 200°-300° C. If cationic polymerization is initiatedwith Lewis acids or Lewis acids in combination with a protogen, highermolecular weights can be achieved. Lewis acid initiators include metalhalides (e.g., AlCl₃, BF₃ , SnCl₄, SbCl₅, ZnCl₂, TiCl₄, PCl₅),organometallic derivatives (e.g. RAlCl₂, R₂ AlCl, R₃ Al), and oxyhalides(e.g., POCl₃, CrO₂ Cl SOCl₂, VOCl₃). Polymerizations with Lewis acidinitiators are generally in solvents at temperatures as low as -100° C.and lower. Other cationic initiators include acetyl perchlorate, iodine,electrolytic initiation, and ionizing radiation.

The monomers of this invention can also be copolymerized withunsaturated monomers that polymerize through their carbon-carbon doublebonds. The monomers that can be used include styrene or alkylsubstituted styrene having 8 to 12 carbon atoms, dienes having 4 to 8carbon atoms, acrylates and alkyl acrylates having 3 to 20 carbon atoms,acrylic acids having 3 to 8 carbon atoms, or acrylonitrile monomershaving 3 to 8 carbon atoms. The weight ratio of monomers of thisinvention to the other comonomers listed above is desirably from about10:90 to 90:10, and preferably from about 30:70 to about 70:30.

Regardless of the type of polymerization, the weight average molecularweight of the various linear polymers of the present invention isgenerally from about 10,000 to about 2,500,000, and preferably fromabout 20,000 to about 1,000,000. Naturally, the molecular weightutilized will often depend upon a desired end use and properties. Thecrosslinked polymers of this invention would higher weights. These canhave high crosslink density.

Numerous different type of monomers exist, only some of which arerepresented by the above formulas II through V. That is, as noted above,the reaction product can yield various blends of monomers or hybridtypes of monomers with specific formulas II through V beingrepresentative of various classes of monomers so produced. With regardto the specific types of formulas, when a monomer of formula II ispolymerized, a polymer is generally produced having the following repeatunit incorporated therein ##STR9## Similarly, the compound of formulaIII when polymerized will have the following repeat unit. ##STR10##Similarly, when a monomer of formula IV is polymerized, the repeat unitwill have the following formula ##STR11## When the monomer of formulaIVB is polymerized, the repeat unit would have the following formula##STR12## When one of the unsaturated groups of the monomer of formulatype VA is polymerized, the repeat unit will have the following formula##STR13## Of course, if the second unsaturated group is polymerized, ahighly crosslinked network or polymer system will be generated.

Similarly, if the unsaturated groups of the monomer of formula type VBis polymerized, the repeat unit would have the following formula##STR14## Of course, it is to be understood that it is within theconcept of the present invention that the above monomers (reactionproduct of isocyanates with aminostyrene) can be polymerized to formhomopolymers or copolymers constituting at least 100 percent of therepeat units, i.e. homopolymer, or can generally constitute anywherefrom about 5 to about 95 percent of a copolymer, desirably from about 20to about 80 percent, with the remainder of the repeat units beinggenerated from one or more of the other comonomers as describedhereinabove which were not made from aminostyrenes.

The above discussed polymers and copolymers as well as the variousblends thereof can further be reacted with various compounds such as anepoxy to yield a graft type polymer.

Although the substituted amino styrene monomers are desirably reactedfirst with an isocyanate and then polymerized, it is also possible tofirst polymerize the aminostyrene into a polymer and then react thependant amino groups with an isocyanate of the formula R(NCO)x. In thatthe NH₂ group may inhibit polymerization, it is anticipated that the NH₂group can be reacted with various protecting groups for the aminefunctionality prior to polymerization and subsequent to polymerizationdeprotected to regenerate the NH₂ group. Thus, a polymer having astructural repeat unit of ##STR15## can be generated from these monomerswith their protecting group. Examples of protecting groups includedansyl chloride forming a dansyl derivative; ketones forming a ketimine;or using a silane forming a trisilyl derivative. The substituted aminostyrene monomers or amine protected derivatives thereof can also becopolymerized with the unsaturated monomers that polymerize throughtheir double bond previously listed. Subsequent to polymerization andany deprotecting reactions for the amines, the polymers are desirablyreacted with the polyisocyanates R(NCO)_(x).

The polymers or copolymers made from monomeric reaction products ofaminostyrenes and isocyanates or blends thereof, or the monomericreaction products themselves, can react with an epoxy resin. Generally,any epoxy resin known to the art and to the literature can be utilized.The amount of epoxy resin which can be reacted with the above polymersor monomers is generally from about 0.1 percent to about 99 percent byweight and desirably from about to 50 to about 95 percent by weight,based upon the total weight of the epoxy resin and the above-notedmonomers or polymers of the present invention. Generally, depending upondesired end use and desired properties, a high amount of monomer orpolymer can be utilized, or a high amount of epoxy, or anything inbetween. The reaction with the epoxy is generally carried out atelevated temperatures as from about 100 to about 250° C., desirably fromabout 125° to about 225° C., and preferably from about 150° to about200° C. Generally, a catalyst is not utilized and the reaction isconducted in an inert atmosphere.

Types of epoxy resins which can be utilized include glycidyl ethers ofbisphenols such as diglycidyl ether of tetrabromobisphenol A; glycidylethers of polynuclear phenols; glycidyl ethers of aliphatic polyols suchas chlorine-containing aliphatic diepoxy and polyepichlorohydrin;glycidyl esters such as aliphatic diacid glycidyl esters and epoxidizedphenolphthalein; glycidyl epoxies containing nitrogen such as glycidylamides and amide-containing epoxies; glycidyl derivatives of cyanuricacid; glycidyl resins from melamines; epoxy resin made from diphenolicacid; glycidyl amines such as triglycidyl ether amine of p-aminophenoland bis(2,3-epoxy -propyl)methylpropylammonium p-toluenesulfonate;glycidyl triazines; thioglycidyl resins such as epoxidized bisulfide;silicon-glycidyl resins such as 1,4-bis[2,3-epoxypropoxy)dimethylsilyl];and fluorine glycidyl resins.

Still other examples of suitable epoxy resins include glycidyl ethers ofnovolac resins such as epoxylated phenol-formaldehyde novolac resin;glycidyl ethers of mono-, di-, and trihydric phenols.

Still further resins are those which are synthesized from mono-epoxiesother than epihalohydrins including epoxy resins made from unsaturatedmonoepoxies such as polyallyl glycidyl ether and glycidyl sorbate dimer;epoxy resins from monoepoxy alcohols; epoxy resins from monoepoxies byester interchange; epoxy resins from glycidyl aldehyde; polyglycidylcompounds containing unsaturation such as allyl-substituted diglycidylether of bisphenol A; epoxy-resin adducts of the above; and epoxy resinswhich are synthesized from olefins and chloroacetyls such as butadienedioxide, vinylcyclohexane dioxide, epoxidized polybutadiene, andbis(2,3-epoxycyclopentyl)ether. A more comprehensive list of epoxyresins can be found in Handbook of Epoxy Resins, by Henry Lee and KrisNeville, McGraw-Hill, Inc., 1967, which is hereby incorporated byreference. A highly preferred epoxy resin is diglycidyl ethers ofbisphenol A (DGEBA) having the following formula: ##STR16## wherein n isan integer from 0 to 100, and preferably from 10 to 20.

The monomers or polymers of this invention can be utilized as a matrixresin either with or without fiber reinforcement. Fillers couldoptionally be used with the matrix resin. Depending on whether themonomers or polymers had residual unreacted double bonds, isocyanategroups, or amine groups, they crosslink, forming a cured product with orwithout other reactive compounds. If they had residual double bonds,they could be crosslinked by the addition of a free radical source aspreviously described for polymerization. If they had unreactedisocyanate groups, they could be crosslinked by adding a secondcomponent reactive with isocyanate groups. These could be polyols,polyamines, polycarboxylic acids, water, or a combination thereof. Theaddition of water to a composition having unreacted isocyanate groupswould result in a foamed product due to the generation of CO₂. Theaddition of difunctional epoxy resins to either the above-mentionedmonomers or polymers derived from aminostyrenes, would result in epoxyterminated epoxy-terminated compounds that can be cured with traditionalepoxy curatives or with additional monomers or polymers derived fromaminostyrene. If monomers derived from aminostyrene are reacted withepoxy resins, the resulting composition can also be cured through freeradical processes. Solvents may be used in the above reactions.

With regard to the matrix resins of the present invention, they can beutilized as various articles such as printed circuit boards, electricalequipment, electrical housings. A preferred area is as an adhesivewherein the above-described reaction products of aminostyrenes andisocyanates are reacted with a diepoxide or polyepoxide resin. These areapplied to a phenolic prepreg paper substrate. More preferably, theepoxy is applied to one surface of the prepregged substrate and themonomers or polymer derived from amino styrenes is applied to a surfaceto a similar substrate. The two substrates are then brought together andunder pressure and heat where a chemical reaction occurs. Thetemperature can be above the melting point of the monomers or from about100° to about 200° C. Such an end use finds great utility in thepreparation of printed circuit boards, especially since the reactedepoxy polymer composition has good vapor barrier resistance.

The fibers used in the prepreg may be Kevlar™, fiberglass, carbonfibers, graphite fibers, pyrolyzed polyacrylonitrile fibers, and otherreinforcing fibers.

The invention will be better understood by reference to the followingexamples.

EXAMPLES Preparation of Derivatives from Aminostyrene

o-Tolyl Urea Styrene: 1.00 g (8.40 mmol) of p-aminostyrene (99% TokyoKasei) was added to a 250 ml round bottom flask containing 10 ml ofchloroform. After ten minutes of mixing, 1.12 g (8.41 mmol) of o-tolylisocyanate (99% Aldrich) was added dropwise. Within seconds, a yellowprecipitate formed. The precipitate was filtered to remove the reactionliquid, then washed with 20 ml of chloroform resulting in pale yellowpowder (1.45 g, 68% crude yield, mp=193° C.).

m-Tolyl Urea Styrene: 1.00 g (8.40 mmol) of p-aminostyrene (99% TokyoKasei) was added to a 250 ml round bottom flask containing 10 ml ofchloroform. After ten minutes of mixing, 1.12 g (8.41 mmol) of m-tolylisocyanate (99% Aldrich) was added dropwise. Within seconds, a white,pinkish precipitate formed. Chloroform (20 ml) was added to aidstirring. The precipitate was filtered to remove the reaction liquid,then washed with 20 ml of chloroform resulting in a white powder (166 g,78% crude yield, mp=203° C.).

p-Tolyl Urea Styrene: 1.00 g (8.40 mmol) of p-aminostyrene (99% TokyoKasei) was added to a 250 ml round bottom flask containing 10 ml ofchloroform. After ten minutes of mixing, 1.12 g (8.41 mmol) of p-tolylisocyanate (99% Aldrich) was added dropwise. Within seconds, a white,pinkish precipitate formed. Chloroform (20 ml) was added to aidstirring. The precipitate was filtered to remove the reaction liquid,then washed with 20 ml of chloroform resulting in a pale yellow powder(1.85 g, 87% crude yield, mp=242° C.).

1,6-Hexyl Urea Styrene Dimer: 1.00 g (8.40 mmol) of p-aminostyrene (99%Tokyo Kasei) was added to a 250 ml round bottom flask containing 100 mlof chloroform. After ten minutes of mixing, 0.706 g (4.20 mmol) of1,6-diisocyanato hexane (98% Aldrich) was added dropwise. After twentyminutes, a white, pinkish precipitate formed. The precipitate wasfiltered to remove the reaction liquid, then washed with 20 ml ofchloroform resulting in a pale white powder (0.87 g, 51% crude yield,mp=228° C.).

n-Butyl Urea Styrene: 1.00 g (8.40 mmol) of p-aminostyrene (99% TokyoKasei) was added to a 250 ml round bottom flask containing 10 ml ofchloroform. After ten minutes of mixing, 0.84 g (8.47 mmol) of n-butylisocyanate (99% Aldrich) was added dropwise. Within seconds, a yellowprecipitate formed. Chloroform (20 ml) was added to aid stirring. Theprecipitate was filtered to remove the reaction liquid, then washed with20 ml of chloroform resulting in a pale yellow powder (1.78 g, 96% crudeyield, mp=116° C.).

n-Octadecyl Urea Styrene: 1.00 g (8.40 mmol) of p-aminostyrene (99%Tokyo Kasei) was added to a 250 ml round bottom flask containing 10 mlof chloroform. After ten minutes of mixing, 2.52 g (8.41 mmol) ofn-octadecyl isocyanate (98% Aldrich) was added dropwise. Within seconds,a yellow precipitate formed. Chloroform (20 ml) was added to aidstirring. The precipitate was filtered to remove the reaction liquid,then washed with 20 ml of chloroform resulting in a pale yellow powder(3.38 g, 96.0% crude yield, mp=109° C.).

1,6-Hexyl Isocyanate Urea Styrene: 1.00 g (8.40 mmol) of p-aminostyrene(99% Tokyo Kasei) was added to a 250 ml round bottom flask containing100 ml of chloroform. After ten minutes of mixing, 1.42 g (8.40 mmol) of1,6-diisocyanato hexane (98% Aldrich) was added dropwise. Within twentyminutes, a yellow precipitate formed. The precipitate was filtered toremove the reaction liquid, then washed with 20 ml chloroform resultingin a pale yellow powder (2.23 g, 92.1% crude yield, mp=91° C.).

Phenyl Urea Styrene: 5.00 g (42.0 mmol) of p-aminostyrene (99% TokyoKasei) was added to a 250 ml round bottom flask. After ten minutes ofmixing, 5.00 g (42.0 mmol) of phenyl isocyanate (99% Aldrich) was addeddropwise. Within seconds, a yellow precipitate formed. Chloroform (20ml) was added to aid stirring. The precipitate was filtered to removethe reaction liquid, then washed with 20 ml of chloroform resulting in apale yellow powder (8.60 g, 86.0 % crude yield, mp=213° C.).

Cross-linking Reactions:

Phenyl urea styrene (0.11 g) was added to DER 31 (0.86 g) in a 10 mlvial. The mixture was heated for one hour at 110° C., resulting in arubbery mass. Upon cooling to room temperature, the mixture hardenedinto an insoluble mass.

Phenyl urea styrene (0.16 g) was added to DER 61 (1.83 g) in a 10 mlvial. The mixture was heated for one hour at 110° C., resulting in arubbery mass Upon cooling to room temperature, the mixture hardened intoa insoluble mass.

Phenyl urea styrene (0.18 g) was added to DER 64 (1.63 g) in a 10 mlvial. The mixture was heated for one hour at 110° C., resulting in arubbery mass. Upon cooling to room temperature, the mixture hardenedinto an insoluble mass.

Phenyl urea styrene (0.20 g) was added to DER 667 (1.95 g) in a 10 mlvial. The mixture was heated for one hour at 110° C., resulting in arubbery mass. Upon cooling to room temperature, the mixture hardenedinto an insoluble mass.

The DER resins are the epoxidized reaction products of epichlorohydrinand bisphenol A as shown in the formula in the text. DER 331 has an nvalue of 0, DER 661 has an n value of 3, DER 664 has an n value of 5 or6, and DER 667 has an n value of 9.

Polymerizations:

Phenyl urea styrene (1.20 mg) was added to a DSC cell. The sample washeated 10° C./min under nitrogen to 50° C. past the melting point(215.6° C.). After the sample cooled to room temperature, the sample washeated 10° C./min to 600° C. showing a Tg at 175° C. and no meltingpoint. FT-IR confirmed the polymerization by the disappearance ofabsorption peaks at the frequencies associated with unsaturation.

o-Tolylureastyrene (2.82 mg) was added to a DSC cell. The sample washeated 10° C./min under nitrogen to 50° C. past the melting point(193.1° C.). After the sample cooled to room temperature, the sample washeated 10° C./min to 600° C. showing a Tg at 200° C. and no meltingpoint. FT-IR confirmed the polymerization by the disappearance ofabsorption peaks at the frequencies associated with unsaturation.

m-Tolylureastyrene (1.54 mg) was added to a DSC cell. The sample washeated 10° C./min under nitrogen to 50° C. past the melting point(203.1° C.). After the sample cooled to room temperature, the sample washeated 10° C./min to 600° C. showing a Tg at 200° C. and no meltingpoint. FT-IR confirmed the polymerization by the disappearance ofabsorption peaks at the frequencies associated with unsaturation.

p-Tolylureastyrene (1.37 mg) was added to a DSC cell. The sample washeated 10° C./min under nitrogen to 50° C. past the melting point(242.4° C.). After the sample cooled to room temperature, the sample washeated 10° C./min to 600° C. showing a Tg at 225° C. and no meltingpoint. FT-IR confirmed the polymerization by the disappearance ofabsorption peaks at the frequencies associated with unsaturation.

Diisohexylureastyrene (1.43) was added to a DSC cell. The sample washeated 10° C./min under nitrogen to 50° C. past the melting point(228.4° C.). After the sample cooled to room temperature, the sample washeated 10° C./min to 600° C. showing a Tg at 250° C. and no meltingpoint. FT-IR confirmed the polymerization by the disappearance ofabsorption peaks at the frequencies associated with unsaturation.

Copolymerization:

Styrene (4.5 g) and phenyl urea styrene (0.5 g) were added to 50 ml ofchloroform. AIBN (5.0 mg) was added and the mixture heated over night atreflux. The resulting copolymer was dried resulting in a rubbery mass(4.7 g, 94% yield). The structure was confirmed by ¹³ C NMR.

While in accordance with the Patent Statutes, the best mode andpreferred embodiment has been set forth, the scope of the invention isnot limited thereto, but rather by the scope of the attached claims.

What is claimed is:
 1. A urea substituted compound, comprising;thereaction product of at least one aminostyrene compound having theformula ##STR17## and at least one polyisocyanate having the formula R²--(NCO)_(x), where x is from about 1 to about 4, and R¹ is H, fluorine,chlorine, iodine, bromine, an alkyl having 1 to 44 carbon atoms, or anaryl or alkyl substituted aryl having 6 to 40 carbon atoms, and R² is analkyl having 2 to 20 carbon atoms, a cycloalkyl having 4 to 20 carbonatoms, an aromatic or an alkyl substituted aromatic having 6 to 20carbon atoms, or an aromatic substituted alkyl having 6 to 20 carbonatoms.
 2. A urea substituted compound according to claim 1, wherein R¹is H or an alkyl having 1 to 8 carbon atoms, R² is an alkyl orcycloalkyl having 4 to 20 carbon atoms or an aromatic or alkylsubstituted aromatic having 6 to 20 carbon atoms or an aromaticsubstituted alkyl having 6 to 20 carbon atoms.
 3. A urea substitutedcompound according to claim 2, wherein the value of x is about 1 and themole ratio of R² --(NCO)_(x) to aminostyrene is from about 0.9 to about1.1.
 4. A urea substituted compound according to claim 1, wherein thereaction product has the formula: ##STR18##
 5. A urea substitutedcompound according to claim 4, wherein R¹ is limited to H or an alkylhaving 1 to 8 carbon atoms, R² is an alkyl having from 2 to 20 carbonatoms, a cycloalkyl having 4 to 20 carbon atoms, an aromatic or an alkylsubstituted aromatic having 6 to 20 carbon atoms, or an aromaticsubstituted alkyl having 6 to 20 carbon atoms.
 6. A urea substitutedcompound according to claim 5, wherein R¹ is H or CH₃, the aminostyrenecompound is para substituted and R² --(NCO)_(x) is a tolyl isocyanate,n-butyl isocyanate, n-octadecyl isocyanate, or phenyl isocyanate.
 7. Aurea substituted compound according to claim 1, wherein the value of xis from about 2 to about 3 and the mole ratio of the R² --(NCO)_(x) tothe aminostyrene compound is from about 0.8 to about 1.8.
 8. A ureasubstituted compound, according to claim 7, wherein the reaction producthas the formula; ##STR19##
 9. A urea substituted compound according toclaim 7, wherein R¹ is H or an alkyl having 1 to 8 carbon atoms, R² isan alkyl having from 2 to 20 carbon atoms, a cycloalkyl having 4 to 20carbon atoms, an aromatic or an alkyl substituted aromatic having 6 to20 carbon atoms, or an aromatic substituted alkyl having 6 to 20 carbonatoms.
 10. A urea substituted compound according to claim 9, wherein R¹is H or CH₃ and the aminostyrene compound has the amino group in thepara position.
 11. A urea substituted compound according to claim 1,wherein the value of x is about 2 and the mole ratio of the R²--(NCO)_(x) to the aminostyrene compound is from about 1.9 to about 4.0.12. A urea substituted compound according to claim 11, wherein thereaction product has the formula; ##STR20##
 13. A urea substitutedcompound according to claim 12, wherein R¹ is H or an alkyl having 1 to8 carbon atoms, R² is an alkyl having from 2 to 20 carbon atoms, acycloalkyl having 4 to 20 carbon atoms, an aromatic or an alkylsubstituted aromatic having 6 to 20 carbon atoms, or an aromaticsubstituted alkyl having 6 to 20 carbon atoms.
 14. A urea substitutedcompound according to claim 13, wherein R¹ is H or CH₃ and theaminostyrene compound has the amino group in the para position.
 15. Aurea substituted compound according to claim 1, wherein the value of xis from about 2 to about and the ratio of R² --(NCO)_(x) to theaminostyrene is from about 0.33 to about 0.78.
 16. A urea substitutedcompound according to claim 15, wherein the reaction product has theformula; ##STR21## and wherein the R³ groups are independently hydrogen,or an alkyl having from 1 to 8 carbon atoms within said formula.
 17. Aurea substituted compound according to claim 16, wherein R¹ is limitedto H or an alkyl having 1 to 8 carbon atoms, R² is an alkyl having from2 to 20 carbon atoms, a cycloalkyl having 4 to 20 carbon atoms, anaromatic or an alkyl substituted aromatic having 6 to 20 carbon atoms,or an aromatic substituted alkyl having 6 to 20 carbon atoms.
 18. A ureasubstituted compound according to claim 17, wherein R¹ is H or CH₃, andthe aminostyrene compound has the amino group in the para position. 19.A polymer made by polymerizing at least one urea substituted compound ofclaim
 1. 20. A polymer made by polymerizing at least one ureasubstituted compound of claim
 4. 21. A polymer made by polymerizing atleast one urea substituted compound of claim
 8. 22. A polymer made bypolymerizing at least one urea substituted compound of claim
 12. 23. Apolymer made by polymerizing at least one urea substituted compound ofclaim
 16. 24. A urea substituted compound, comprising;the reactionproduct of at least one aminostyrene compound having the formula##STR22## and at least one reacted polyisocyanate, said at least onereacted polyisocyanate being the reaction product of polyols orpolyamines having molecular weights of less than 300 with polyisocyanteshaving the formula R² --(NCO)_(x), where x is from about 2 to about 4,and R¹ is H, fluorine, chlorine, iodine, bromine, an alkyl having 1 to44 carbon atoms, or an aryl or alkyl substituted aryl having 6 to 40carbon atoms, and R² is an alkyl having 2 to 20 carbon atoms, acycloalkyl having 4 to 20 carbon atoms, an aromatic or an alkylsubstituted aromatic having 6 to 20 carbon atoms, or an aromaticsubstituted alkyl having 6 to 20 carbon atoms.
 25. A urea substitutedcompound according to claim 24, wherein the aminostyrene compound hasthe amino group in the para position, wherein R¹ is H or methyl andwherein x is from about 2 to about
 3. 26. A thermoset compositioncomprising;the reaction product of a polymer and one or morepolyisocyanates, said polymer having as at least one of its structuralrepeat units ##STR23## wherein R¹ is H, fluorine, chlorine, bromine, analkyl having 1 to 44 carbon atoms, or an aryl or alkyl substituted arylhaving from 6 to 40 carbon atoms, said one or more polyisocyanateshaving the formula R² --(NCO)_(x), wherein x is from about 1 to about 4,wherein R² is an alkyl having from 2 to 20 carbon atoms, a cycloalkylhaving from 4 to 20 carbon atoms, an aromatic or alkyl substitutedaromatic having from 6 to 20 carbon atoms, or an aromatic substitutedalkyl having from 6 to 20 carbon atoms.
 27. A composition according toclaim 26, including at least one polyol comprising polyethers orpolyesters.
 28. A composition according to claim 26, wherein saidaminostyrene monomer or said polymer with one of its structural unitsbeing ##STR24## has its respective amino in the para position on thearomatic ring and R¹ is H or CH₃.